Polyisocyanates from fused bicyclic polyols and polyurethanes therefrom

ABSTRACT

The present invention is directed to polyisocyanates and polyurethanes derived therefrom. In various embodiments, the present invention provides polyisocyanates, methods of making the polyisocyanates from fused bicyclic alcohols, polyurethanes, and methods of making the polyurethanes from the polyisocyanates.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/434,710, filed Apr. 9, 2015, which is a U.S. National Stage Filingunder 35 U.S.C. 371 from International Application No.PCT/US2013/064972, filed on 15 Oct. 2013 and published as WO 2014/062631on 24 Apr. 2014, which claims the benefit of priority to U.S.Provisional Patent Application Ser. No. 61/713,889 entitled“POLYISOCYANATES FROM FUSED BICYCLIC POLYOLS AND POLYURETHANESTHEREFROM,” filed Oct. 15, 2012, and also claims the benefit of priorityto U.S. Provisional Patent Application Ser. No. 61/872,116 entitled“TACKIFIER COMPOUNDS AND METHODS OF USING THE SAME,” filed Aug. 30,2013, which applications and publications are incorporated herein intheir entirety by reference.

BACKGROUND OF THE INVENTION

Polyurethanes are a versatile class of polymers that are used in a widerange of applications, for example: plastics, elastomers, flexible orrigid foams, gaskets and seals, coatings, fibers, and adhesives.Polyurethanes can be made by combining polyols and polyisocyanates, suchas diisocyanates, optionally including chain-extenders such as diols,diamines, and the like. Polyols and polyisocyanates are typicallyderived from petroleum-based materials. There has been work in recentyears to replace the petroleum-derived polyols with polyols derived fromnon-petroleum sources, such as vegetable oil, soybean oil, and castoroil. However, little attention has been paid to development ofpolyisocyanates from renewable non-petroleum sources.

SUMMARY OF THE INVENTION

The present invention is directed to polyisocyanates derived from fusedbicyclic alcohols, such as isosorbides, and polyurethanes derivedtherefrom.

In various embodiments, the polyisocyanates and polyurethanes of thepresent invention have advantages over other polyisocyanates andpolyurethanes, some of which are unexpected. Past attempts to convertfused bicyclic alcohols into a biorenewable polyisocyanates have eitherbeen low-yielding or required a relatively large amount of expensivecatalysts; however, various embodiments of the present method ofpreparing a polyisocyanate from a fused polyol and an acid anhydride canbe more environmentally friendly (e.g. benign) and cost effective.

The present invention provides novel polyisocyanates and polyurethanesderived therefrom. In some examples, the polyisocyanates areadvantageously derived primarily from non-petroleum based materials. Insome embodiments, the polyisocyanates can be made usingenvironmentally-friendly techniques, with some or all synthetic stepsavoiding or limiting at least one of wasted materials, wasted energy,and the use of toxic or petroleum-derived reagents. In some examples,the polyisocyanates of the present invention can be made at lower costthan other polyisocyanates. In some embodiments, time-consumingpurification procedures such as chromatography can be avoided andinstead crude material can be used in subsequent steps or facile andeasily scalable vacuum distillation can be used for purification. Invarious embodiments, the polyurethanes of the present invention can formaqueous dispersions more effectively than other polyurethanes, allowingthe application of polyurethanes without the use of or with reduced useof environmentally harmful and toxic volatile organic solvents.

In various embodiments, the polyisocyanates can be used to generatepolyurethanes using a more environmentally-friendly synthesis and usingless toxic materials than polyurethanes made from other polyisocyanates.In some examples, the polyisocyanates of the present invention can beused to synthesize polyurethanes at lower cost than polyurethanessynthesized from other polyisocyanates. The polyurethanes of the presentinvention can have characteristics that advantageously distinguish overother polyurethanes, including at least one of better strength, betterrigidity, better melting properties, more biorenewably derived, greaterbiodegradability, better ability to form aqueous dispersions, and lowercost. For example, in various embodiments, the fused cyclicpolyisocyanates can provide polyurethanes that are more rigid than othernon-cyclic isocyanates, including those derived from fatty acids.

In various embodiments, the present invention provides a compound ofFormula (I):

In Formula (I), fused rings A and B are each independently selected from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and n areeach independently 1-8. The variable R′ is selected from the groupconsisting of (C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and(C₂-C₁₀)alkynylene, and R′ is unsubstituted or substituted with at leastone J. The variable R″ is selected from the group consisting of —C(O)OH,—C(O)O⁻X⁺, —C(O)F, —C(O)Cl, —C(O)Br, —C(O)I, —C(O)N₃, and —NCO, whereinX⁺ is a counterion. In Formula (I), fused rings A and B are eachindependently unsubstituted or substituted with at least one of J,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy,(C₁-C₁₀)haloalkoxy, (C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl,(C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl, (C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or(C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; wherein each alkyl, alkenyl, alkynyl,haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, andheteroaryl is independently unsubstituted or further substituted with atleast one J. In Formula (I), J independently at each occurrence isselected from the group consisting of F, Cl, Br, I, OR, CN, CF₃, OCF₃,R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R,SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR,OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R,N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

In various embodiments, the present invention provides a method ofmaking a polyisocyanate. The method includes contacting a compoundhaving the structure

and an acid anhydride having the structure

The contacting of the compound and the acid anhydride provides apolyacid having the structure of Formula (I)

In the structure of Formula (I), R″ is —C(O)OH. The method also includescontacting the polyacid and an acyl halide generator. Contacting thepolyacid and the acyl halide generator provides a polyacid halide havingthe structure of Formula (I) where R″ is —C(O)X, wherein X is halide.The method also includes contacting the polyacid halide and an azidegenerator under conditions suitable to provide a polyisocyanate havingthe structure of Formula (I) where R″ is —NCO. In the structure ofFormula (I), fused rings A and B are each independently selected from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and n areeach independently 1-8. The variable R′ is selected from the groupconsisting of (C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and(C₂-C₁₀)alkynylene, where R′ is unsubstituted or substituted with atleast one J. In the structure of Formula (I), fused rings A and B areeach independently unsubstituted or substituted with at least one of J,(C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl,(C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy, (C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl,(C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl, (C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or(C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; wherein each alkyl, alkenyl, alkynyl,haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, andheteroaryl is independently unsubstituted or further substituted with atleast one J. In Formula (I), J independently at each occurrence isselected from the group consisting of F, Cl, Br, I, OR, CN, CF₃, OCF₃,R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R,SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR,OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R,N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

In various embodiments, the present invention provides a polyurethanecomprising a plurality of subunits each having the structure of Formula(II)

In Formula (II), fused rings A and B are each independently selectedfrom (C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl. The variables m and nare each independently 1-8. The variable R′ is selected from the groupconsisting of (C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and(C₂-C₁₀)alkynylene, where R′ is unsubstituted or substituted with atleast one J. In Formula (II), fused rings A and B are each independentlyunsubstituted or substituted with at least one of J, (C₁-C₁₀)alkyl,(C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy,(C₁-C₁₀)haloalkoxy, (C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl,(C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl, (C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or(C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; where each alkyl, alkenyl, alkynyl,haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, andheteroaryl is independently unsubstituted or further substituted with atleast one J. In Formula (II), J independently at each occurrence isselected from the group consisting of F, Cl, Br, I, OR, CN, CF₃, OCF₃,R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, S(O)R,SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR,OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂NHC(O)R,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂, N(R)SO₂R,N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, where R is independently at each occurrence selected from thegroup consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g.,0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.In addition, it is to be understood that the phraseology or terminologyemployed herein, and not otherwise defined, is for the purpose ofdescription only and not of limitation. Any use of section headings isintended to aid reading of the document and is not to be interpreted aslimiting; information that is relevant to a section heading may occurwithin or outside of that particular section. Furthermore, allpublications, patents, and patent documents referred to in this documentare incorporated by reference herein in their entirety, as thoughindividually incorporated by reference. In the event of inconsistentusages between this document and those documents so incorporated byreference, the usage in the incorporated reference should be consideredsupplementary to that of this document; for irreconcilableinconsistencies, the usage in this document controls.

In the methods of manufacturing described herein, the steps can becarried out in any order without departing from the principles of theinvention, except when a temporal or operational sequence is explicitlyrecited.

Furthermore, specified steps can be carried out concurrently unlessexplicit claim language recites that they be carried out separately. Forexample, a claimed step of doing X and a claimed step of doing Y can beconducted simultaneously within a single operation, and the resultingprocess will fall within the literal scope of the claimed process.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range. When a range or a list ofsequential values is given, unless otherwise specified any value withinthe range or any value between the given sequential values, and theendpoints of any sequence or range, is also disclosed.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “organic group” as used herein refers to but is not limited toany carbon-containing functional group. For example, anoxygen-containing group such as alkoxy groups, aryloxy groups,aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups includingcarboxylic acids, carboxylates, and carboxylate esters; asulfur-containing group such as alkyl and aryl sulfide groups; and otherheteroatom-containing groups. Non-limiting examples of organic groupsinclude OR′, OC(O)N(R′)₂, CN, CF₃, OCF₃, R′, C(O), methylenedioxy,ethylenedioxy, N(R′)₂, SR′, SOR′, SO₂R′, SO₂N(R′)₂, SO₃R′, C(O)R′,C(O)C(O)R′, C(O)CH₂C(O)R′, C(S)R′, C(O)OR′, OC(O)R′, C(O)N(R′)₂,OC(O)N(R′)₂, C(S)N(R′)₂, (CH₂)₀₋₂N(R′)C(O)R′, (CH₂)₀₋₂N(R′)N(R′)₂,N(R′)N(R′)C(O)R′, N(R′)N(R′)C(O)OR′, N(R′)N(R′)CON(R′)₂, N(R′)SO₂R′,N(R′)SO₂N(R′)₂, N(R′)C(O)OR′, N(R′)C(O)R′, N(R′)C(S)R′, N(R′)C(O)N(R′)₂,N(R′)C(S)N(R′)₂, N(COR′)COR′, N(OR′)R′, C(═NH)N(R′)₂, C(O)N(OR′)R′, orC(═NOR′)R′ wherein R′ can be hydrogen (in examples that include othercarbon atoms) or a carbon-based moiety, and wherein the carbon-basedmoiety can itself be further substituted; for example, wherein R′ can behydrogen (in examples that include other carbon atoms), alkyl, acyl,cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl,wherein any alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl,heteroaryl, or heteroarylalkyl, or R′ can be independently mono- ormulti-substituted with J; or wherein two R′ groups bonded to a nitrogenatom or to adjacent nitrogen atoms can together with the nitrogen atomor atoms form a heterocyclyl, which can be mono- or independentlymulti-substituted with J. Examples of organic groups include linearand/or branched groups such as alkyl groups, fully or partiallyhalogen-substituted haloalkyl groups, alkenyl groups, alkynyl groups,aromatic groups, acrylate functional groups, and methacrylate functionalgroups; and other organic functional groups such as ether groups,cyanate ester groups, ester groups, carboxylate salt groups, and maskedisocyano groups. Examples of organic groups include, but are not limitedto, alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl,s-butyl, and t-butyl groups, acrylate functional groups such asacryloyloxypropyl groups and methacryloyloxypropyl groups; alkenylgroups such as vinyl, allyl, and butenyl groups; alkynyl groups such asethynyl and propynyl groups; aromatic groups such as phenyl, tolyl, andxylyl groups; cyanoalkyl groups such as cyanoethyl and cyanopropylgroups; halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl,3-chloropropyl, dichlorophenyl, and 6,6,6,5,5,4,4,3,3-nonafluorohexylgroups; alkenyloxypoly(oxyalkyene) groups such asallyloxy(polyoxyethylene), allyloxypoly(oxypropylene), andallyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups;alkyloxypoly(oxyalkyene) groups such as propyloxy(polyoxyethylene),propyloxypoly(oxypropylene), andpropyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; halogensubstituted alkyloxypoly(oxyalkyene) groups such asperfluoropropyloxy(polyoxyethylene),perfluoropropyloxypoly(oxypropylene), andperfluoropropyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups;alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,and ethylhexyloxy groups; aminoalkyl groups such as 3-aminopropyl,6-aminohexyl, 11-aminoundecyl, 3-(N-allylamino)propyl,N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl,p-aminophenyl, 2-ethylpyridine, and 3-propylpyrrole groups; epoxyalkylgroups such as 3-glycidoxypropyl, 2-(3,4,-epoxycyclohexyl)ethyl, and5,6-epoxyhexyl groups; ester functional groups such as actetoxyethyl andbenzoyloxypropyl groups; hydroxy functional groups such as2-hydroxyethyl groups; masked isocyanate functional groups such aspropyl-t-butylcarbamate, and propylethylcarbamate groups; aldehydefunctional groups such as undecanal and butyraldehyde groups; anhydridefunctional groups such as 3-propyl succinic anhydride and 3-propylmaleic anhydride groups; and metal salts of carboxylic acids such as thezinc, sodium, or potassium salts of 3-carboxypropyl and 2-carboxyethyl.

The term “substituted” as used herein refers to an organic group asdefined herein or molecule in which one or more hydrogen atoms containedtherein are replaced by one or more non-hydrogen atoms. The term“functional group” or “substituent” as used herein refers to a groupthat can be or is substituted onto a molecule, or onto an organic group.Examples of substituents or functional groups include, but are notlimited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groupssuch as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxygroups, oxo(carbonyl) groups, carboxyl groups including carboxylicacids, carboxylates, and carboxylate esters; a sulfur atom in groupssuch as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups,sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atomin groups such as amines, hydroxylamines, nitriles, nitro groups,N-oxides, hydrazides, azides, and enamines; and other heteroatoms invarious other groups. Non-limiting examples of substituents J that canbe bonded to a substituted carbon (or other) atom include F, Cl, Br, I,OR′, OC(O)N(R′)₂, CN, NO, NO₂, ONO₂, azido, CF₃, OCF₃, R′, O (oxo), S(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R′)₂, SR′, SOR′,SO₂R′, SO₂N(R′)₂, SO₃R′, C(O)R′, C(O)C(O)R′, C(O)CH₂C(O)R′, C(S)R′,C(O)OR′, OC(O)R′, C(O)N(R′)₂, OC(O)N(R′)₂, C(S)N(R′)₂,(CH₂)O₂N(R′)C(O)R′, (CH₂)₀₋₂N(R′)N(R′)₂, N(R′)N(R′)C(O)R′,N(R′)N(R′)C(O)OR′, N(R′)N(R′)CON(R′)₂, N(R′)SO₂R′, N(R′)SO₂N(R′)₂,N(R′)C(O)OR′, N(R′)C(O)R′, N(R′)C(S)R′, N(R′)C(O)N(R′)₂,N(R′)C(S)N(R′)₂, N(COR′)COR′, N(OR′)R′, C(═NH)N(R′)₂, C(O)N(OR′)R′, orC(═NOR′)R′ wherein R′ can be hydrogen or a carbon-based moiety, andwherein the carbon-based moiety can itself be further substituted; forexample, wherein R′ can be hydrogen, alkyl, acyl, cycloalkyl, aryl,aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl, wherein anyalkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, orheteroarylalkyl or R′ can be independently mono- or multi-substitutedwith J; or wherein two R′ groups bonded to a nitrogen atom or toadjacent nitrogen atoms can together with the nitrogen atom or atomsform a heterocyclyl, which can be mono- or independentlymulti-substituted with J.

The term “alkyl” as used herein refers to straight chain and branchedalkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from1 to 8 carbon atoms. Examples of straight chain alkyl groups includethose with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples ofbranched alkyl groups include, but are not limited to, isopropyl,iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompassesn-alkyl, isoalkyl, and anteisoalkyl groups as well as other branchedchain forms of alkyl. Representative substituted alkyl groups can besubstituted one or more times with any of the groups listed herein, forexample, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, andhalogen groups.

The term “alkenyl” as used herein refers to straight and branched chainand cyclic alkyl groups as defined herein, except that at least onedouble bond exists between two carbon atoms. Thus, alkenyl groups havefrom 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12carbons or, in some embodiments, from 2 to 8 carbon atoms. Examplesinclude, but are not limited to vinyl, —CH═CH(CH₃), —CH═C(CH₃)₂,—C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂, cyclohexenyl,cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienylamong others.

The term “alkynyl” as used herein refers to straight and branched chainalkyl groups, except that at least one triple bond exists between twocarbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 toabout 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments,from 2 to 8 carbon atoms. Examples include, but are not limited to—C≡CH, —C≡C(CH₃), —C≡C(CH₂CH₃), —CH₂C≡CH, —CH₂C≡C(CH₃), and—CH₂C≡C(CH₂CH₃) among others.

The term “acyl” as used herein refers to a group containing a carbonylmoiety wherein the group is bonded via the carbonyl carbon atom. Thecarbonyl carbon atom is also bonded to another carbon atom, which can bepart of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl,heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group orthe like. In the special case wherein the carbonyl carbon atom is bondedto a hydrogen, the group is a “formyl” group, an acyl group as the termis defined herein. An acyl group can include 0 to about 12-20 or 12-40additional carbon atoms bonded to the carbonyl group. An acyl group caninclude double or triple bonds within the meaning herein. An acryloylgroup is an example of an acyl group. An acyl group can also includeheteroatoms within the meaning here. A nicotinoyl group(pyridyl-3-carbonyl) group is an example of an acyl group within themeaning herein. Other examples include acetyl, benzoyl, phenylacetyl,pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When thegroup containing the carbon atom that is bonded to the carbonyl carbonatom contains a halogen, the group is termed a “haloacyl” group. Anexample is a trifluoroacetyl group.

The term “cycloalkyl” as used herein refers to cyclic alkyl groups suchas, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, thecycloalkyl group can have 3 to about 8-12 ring members, whereas in otherembodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or7. Cycloalkyl groups further include polycyclic cycloalkyl groups suchas, but not limited to, norbornyl, adamantyl, bornyl, camphenyl,isocamphenyl, and carenyl groups, and fused rings such as, but notlimited to, decalinyl, and the like. Cycloalkyl groups also includerings that are substituted with straight or branched chain alkyl groupsas defined herein. Representative substituted cycloalkyl groups can bemono-substituted or substituted more than once, such as, but not limitedto, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstituted cyclohexyl groups ormono-, di- or tri-substituted norbornyl or cycloheptyl groups, which canbe substituted with, for example, amino, hydroxy, cyano, carboxy, nitro,thio, alkoxy, and halogen groups. The term “cycloalkenyl” alone or incombination denotes a cyclic alkenyl group.

The term “aryl” as used herein refers to cyclic aromatic hydrocarbonsthat do not contain heteroatoms in the ring. Thus aryl groups include,but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl,indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl,naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.In some embodiments, aryl groups contain about 6 to about 14 carbons inthe ring portions of the groups. Aryl groups can be unsubstituted orsubstituted, as defined herein. Representative substituted aryl groupscan be mono-substituted or substituted more than once, such as, but notlimited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substitutednaphthyl groups, which can be substituted with carbon or non-carbongroups such as those listed herein.

The term “aralkyl” as used herein refers to alkyl groups as definedherein in which a hydrogen or carbon bond of an alkyl group is replacedwith a bond to an aryl group as defined herein. Representative aralkylgroups include benzyl and phenylethyl groups and fused(cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. Aralkenyl groupare alkenyl groups as defined herein in which a hydrogen or carbon bondof an alkyl group is replaced with a bond to an aryl group as definedherein.

The term “heterocyclyl” as used herein refers to aromatic andnon-aromatic ring compounds containing 3 or more ring members, of which,one or more is a heteroatom such as, but not limited to, N, O, and S.Thus a heterocyclyl can be a cycloheteroalkyl, or a heteroaryl, or ifpolycyclic, any combination thereof. In some embodiments, heterocyclylgroups include 3 to about 20 ring members, whereas other such groupshave 3 to about 15 ring members. A heterocyclyl group designated as aC₂-heterocyclyl can be a 5-ring with two carbon atoms and threeheteroatoms, a 6-ring with two carbon atoms and four heteroatoms and soforth. Likewise a C₄-heterocyclyl can be a 5-ring with one heteroatom, a6-ring with two heteroatoms, and so forth. The number of carbon atomsplus the number of heteroatoms sums up to equal the total number of ringatoms. A heterocyclyl ring can also include one or more double bonds. Aheteroaryl ring is an embodiment of a heterocyclyl group. The phrase“heterocyclyl group” includes fused ring species including those thatinclude fused aromatic and non-aromatic groups. For example, adioxolanyl ring and a benzdioxolanyl ring system (methylenedioxyphenylring system) are both heterocyclyl groups within the meaning herein. Thephrase also includes polycyclic ring systems containing a heteroatomsuch as, but not limited to, quinuclidyl. Heterocyclyl groups can beunsubstituted, or can be substituted as discussed herein. Heterocyclylgroups include, but are not limited to, pyrrolidinyl, piperidinyl,piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl,benzofuranyl, dihydrobenzofuranyl, indolyl, dihydroindolyl, azaindolyl,indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl,benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl,thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl,isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinylgroups.

Representative substituted heterocyclyl groups can be mono-substitutedor substituted more than once, such as, but not limited to, piperidinylor quinolinyl groups, which are 2-, 3-, 4-, 5-, or 6-substituted, ordisubstituted with groups such as those listed herein.

The term “heteroaryl” as used herein refers to aromatic ring compoundscontaining 5 or more ring members, of which, one or more is a heteroatomsuch as, but not limited to, N, O, and S; for instance, heteroaryl ringscan have 5 to about 8-12 ring members. A heteroaryl group is a varietyof a heterocyclyl group that possesses an aromatic electronic structure.A heteroaryl group designated as a C₂-heteroaryl can be a 5-ring withtwo carbon atoms and three heteroatoms, a 6-ring with two carbon atomsand four heteroatoms and so forth. Likewise a C₄-heteroaryl can be a5-ring with one heteroatom, a 6-ring with two heteroatoms, and so forth.The number of carbon atoms plus the number of heteroatoms sums up toequal the total number of ring atoms. Heteroaryl groups include, but arenot limited to, groups such as pyrrolyl, pyrazolyl, triazolyl,tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl,benzothiophenyl, benzofuranyl, indolyl, azaindolyl, indazolyl,benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl,benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl,thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl,isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinylgroups. Heteroaryl groups can be unsubstituted, or can be substitutedwith groups as is discussed herein. Representative substitutedheteroaryl groups can be substituted one or more times with groups suchas those listed herein.

Additional examples of aryl and heteroaryl groups include but are notlimited to phenyl, biphenyl, indenyl, naphthyl (1-naphthyl, 2-naphthyl),N-hydroxytetrazolyl, N-hydroxytriazolyl, N-hydroxyimidazolyl,anthracenyl (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophenyl(2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), indolyl, oxadiazolyl,isoxazolyl, quinazolinyl, fluorenyl, xanthenyl, isoindanyl, benzhydryl,acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), pyrazolyl (3-pyrazolyl),imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl),triazolyl (1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl 1,2,3-triazol-4-yl,1,2,4-triazol-3-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl),thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl,3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3-pyridazinyl,4-pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl,4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl(1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl,6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), benzo[b]furanyl(2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl,5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl),2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl),3-(2,3-dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl),5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl),7-(2,3-dihydro-benzo[b]furanyl), benzo[b]thiophenyl(2-benzo[b]thiophenyl, 3-benzo[b]thiophenyl, 4-benzo[b]thiophenyl,5-benzo[b]thiophenyl, 6-benzo[b]thiophenyl, 7-benzo[b]thiophenyl),2,3-dihydro-benzo[b]thiophenyl, (2-(2,3-dihydro-benzo[b]thiophenyl),3-(2,3-dihydro-benzo[b]thiophenyl), 4-(2,3-dihydro-benzo[b]thiophenyl),5-(2,3-dihydro-benzo[b]thiophenyl), 6-(2,3-dihydro-benzo[b]thiophenyl),7-(2,3-dihydro-benzo[b]thiophenyl), indolyl (1-indolyl, 2-indolyl,3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole(1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl,7-indazolyl), benzimidazolyl (1-benzimidazolyl, 2-benzimidazolyl,4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl,8-benzimidazolyl), benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl),benzothiazolyl (1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl,5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl(1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl),5H-dibenz[b,f]azepine (5H-dibenz[b,f]azepin-1-yl,5H-dibenz[b,f]azepine-2-yl, 5H-dibenz[b,f]azepine-3-yl,5H-dibenz[b,f]azepine-4-yl, 5H-dibenz[b,f]azepine-5-yl),10,11-dihydro-5H-dibenz[b,f]azepine(10,11-dihydro-5H-dibenz[b,f]azepine-1-yl,10,11-dihydro-5H-dibenz[b,f]azepine-2-yl,10,11-dihydro-5H-dibenz[b,f]azepine-3-yl,10,11-dihydro-5H-dibenz[b,f]azepine-4-yl,10,11-dihydro-5H-dibenz[b,f]azepine-5-yl), and the like.

The term “heterocyclylalkyl” as used herein refers to alkyl groups asdefined herein in which a hydrogen or carbon bond of an alkyl group asdefined herein is replaced with a bond to a heterocyclyl group asdefined herein.

Representative heterocyclyl alkyl groups include, but are not limitedto, furan-2-yl methyl, furan-3-yl methyl, pyridine-3-yl methyl,tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl.

The term “heteroarylalkyl” as used herein refers to alkyl groups asdefined herein in which a hydrogen or carbon bond of an alkyl group isreplaced with a bond to a heteroaryl group as defined herein.

The term “alkoxy” as used herein refers to an oxygen atom connected toan alkyl group, including a cycloalkyl group, as are defined herein.Examples of linear alkoxy groups include but are not limited to methoxy,ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples ofbranched alkoxy include but are not limited to isopropoxy, sec-butoxy,tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclicalkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can includeone to about 12-20 or about 12-40 carbon atoms bonded to the oxygenatom, and can further include double or triple bonds, and can alsoinclude heteroatoms. For example, an allyloxy group is an alkoxy groupwithin the meaning herein. A methoxyethoxy group is also an alkoxy groupwithin the meaning herein, as is a methylenedioxy group in a contextwhere two adjacent atoms of a structures are substituted therewith.

The term “amine” as used herein refers to primary, secondary, andtertiary amines having, e.g., the formula N(group)₃ wherein each groupcan independently be H or non-H, such as alkyl, aryl, and the like.Amines include but are not limited to R—NH₂, for example, alkylamines,arylamines, alkylarylamines; R₂NH wherein each R is independentlyselected, such as dialkylamines, diarylamines, aralkylamines,heterocyclylamines and the like; and R₃N wherein each R is independentlyselected, such as trialkylamines, dialkylarylamines, alkyldiarylamines,triarylamines, and the like. The term “amine” also includes ammoniumions as used herein.

The term “amino group” as used herein refers to a substituent of theform —NH₂, —NHR, —NR₂, —NR₃ ⁺, wherein each R is independently selected,and protonated forms of each, except for —NR₃ ⁺, which cannot beprotonated. Accordingly, any compound substituted with an amino groupcan be viewed as an amine. An “amino group” within the meaning hereincan be a primary, secondary, tertiary or quaternary amino group. An“alkylamino” group includes a monoalkylamino, dialkylamino, andtrialkylamino group.

The terms “halo” or “halogen” or “halide”, as used herein, by themselvesor as part of another substituent mean, unless otherwise stated, afluorine, chlorine, bromine, or iodine atom, preferably, fluorine,chlorine, or bromine.

The term “haloalkyl” group, as used herein, includes mono-halo alkylgroups, poly-halo alkyl groups wherein all halo atoms can be the same ordifferent, and per-halo alkyl groups, wherein all hydrogen atoms arereplaced by halogen atoms, such as fluoro. Examples of haloalkyl includetrifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl,1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

The term “hydrocarbon” as used herein refers to a functional group ormolecule that includes carbon and hydrogen atoms. The term can alsorefer to a functional group or molecule that normally includes bothcarbon and hydrogen atoms but wherein all the hydrogen atoms aresubstituted with other functional groups.

The term “independently selected from” as used herein refers toreferenced groups being the same, different, or a mixture thereof,unless the context clearly indicates otherwise. Thus, under thisdefinition, the phrase “X¹, X², and X³ are independently selected fromnoble gases” would include the scenario where, for example, X¹, X², andX³ are all the same, where X¹, X², and X³ are all different, where X¹and X² are the same but X³ is different, and other analogouspermutations.

The term “room temperature” as used herein refers to ambienttemperature, which can be, for example, between about 15° C. and about28° C.

The term “polyisocyanate” as used herein refers to a compound havingmore than one isocyanate moiety, for example, a diisocyanate,triisocyanate, tetraisocyanate, and the like.

The term “polyol” as used herein refers to a compound having more thanone alcohol moiety, for example, a diol, triol, tetraol, and the like.

The term “polyurethane” as used herein refers to a polymer including arepeating unit that includes a carbamate moiety, e.g., —OC(O)—NH—.

Compound of Formula (I).

In various embodiments, the present invention provides a compound ofFormula (I):

Formula (I) includes fused rings A and B, which share a singlecarbon-carbon bond. Rings A and B can be the same or different, and areeach independently selected from (C₅-C₁₀)cycloalkyl and(C₂-C₁₀)heterocyclyl, wherein the designated number of carbon atomsincludes the two carbon atoms that are shared by rings A and B. In someexamples, rings A and B can be the same size, and can both becyclopentyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclononyl, orcyclodecyl. The two hydrogen atoms at the points of fusion can have anysuitable stereochemical configuration with respect to each other andwith respect to other functional groups on rings A and B, and can be synor anti.

Rings A and B can have any suitable number and variety of functionalgroups thereon. Rings A and B each include one or more estersubstituents having the formula R′—R′—C(O)O—. The variables m and n areeach independently 1-8; thus, Rings A and B can each independently haveabout 1 to 8 ester substituents thereon. The variables m and n can havedifferent values, or the variable m and n can be equal. The variables mand n can each be 1. Rings A and B can each have the same type andnumber of ester substituents or a different type and number of estersubstituents. Rings A and B each have at least one ester substituent. Insome examples, fused rings A and B can be each independentlyunsubstituted with the exception of the ester substituents having theformula R″—R′—C(O)O—.

In some examples, fused rings A and B can be each independentlysubstituted with at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl,(C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J. The variable J independently ateach occurrence is selected from the group consisting of F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

In Formula (I), the variable R′ in the ester substituent is selectedfrom the group consisting of (C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and(C₂-C₁₀)alkynylene. In some examples, R′ can be unsubstituted, and inother examples, R′ can be substituted with at least one J, as definedherein. In various examples, R′ can be ethanylene (—CH₂—CH₂—),propanylene (—CH₂—CH₂—CH₂—), or butanylene (—CH₂—CH₂—CH₂—CH₂—).

In Formula (I), the variable R″ is selected from the group consisting of—C(O)OH, —C(O)O⁻X⁺, —C(O)F, —C(O)Cl, —C(O)Br, —C(O)I, —C(O)N₃, and —NCO,wherein X⁺ is a counterion; thus, in embodiments where m=n=1, Formula(I) can represent a diacid, a diacid salt, a diacyl fluoride, a diacylchloride, a diacyl bromide, a diacyl iodide, a diacyl azide, or adiisocyanate, respectively. The variable X⁺ can be any suitablecounterion bearing a +1 charge. For example, X⁺ can be a group I elementsuch as Na⁺ or K⁺, Ag⁺, or NH₄ ⁺. In some embodiments, multiple —O—groups can have a single counterion having a greater than +1 charge, forexample Al³⁺, Ca²⁺, Cu², Fe²⁺, Fe³⁺, or Mg²⁺. In some embodiments,R″=—NCO and Formula (I) represents a polyisocyanate.

In some embodiments, at least one of the ester substituents having theformula R″—R′—C(O)O— is alpha to a carbon atom shared by rings A and B,for example, R″—R′—C(O)O— is bound to an atom of ring A or B that isbound to a carbon atom shared by rings A and B. In some examples, atleast one ester substituent having the formula R″—R′—C(O)O— on each ofrings A and B is alpha to a carbon atom shared by rings A and B. In someexamples, an ester substituent having the formula R″—R′—C(O)O— on ring Ais alpha to a carbon atom shared by rings A and B, and an estersubstituent having the formula R′—R′—C(O)O— on ring B is alpha to theother carbon atom shared by rings A and B, and m can equal n or both mand n can equal 1.

In some examples, at least one of rings A and B include at least oneoxygen atom. In some embodiments, each of rings A and B include at leastone oxygen atom. In some examples, each of rings A and B is atetrahydrofuran ring (e.g. cyclotetramethylene oxide, having anysuitable substituents), where each of the two carbon atoms shared byrings A and B is alpha to the oxygen atom in at least one of rings A andB. In some examples, each of rings A and B is a tetrahydrofuran ring,where one the two carbon atoms shared by rings A and B is alpha to theoxygen atom in ring A, and the other carbon atom shared by rings A and Bis alpha to the oxygen atom in ring B.

In some embodiments, m and n are 1, and each of rings A and B includesat least one oxygen atom, such that one the two carbon atoms shared byrings A and B is alpha to the at least one oxygen atom in ring A andalpha to the ester substituent having the formula R″—R′—C(O)O—substituted on ring B, and the other carbon atom shared by rings A and Bis alpha to the at least one oxygen atom in ring B and alpha to theester substituent having the formula R″—R′—C(O)O— substituted on ring A.

In various embodiments, the compound of Formula (I) is a diisocyanatehaving the following structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving the following structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isosorbide ring system, having the structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isosorbide ring system, where R′ is ethanylene,having the structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isomannide ring system, having the structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isomannide ring system, where R′ is ethanylene,having the structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isoidide ring system, having the structure:

In various embodiments, the compound of Formula (I) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isoidide ring system, where R′ is ethanylene,having the structure:

Method of Making a Polyisocyanate.

In various embodiments, the present invention provides a method ofmaking the compound of Formula (I). The present invention providesembodiments of both the compound of Formula (I) and also a method ofmaking the compound of Formula (I) that encompass any suitable method ofmaking the compound of Formula (I); the compound of Formula (I) is to beunderstood as not limited by any particular method of making thecompound.

In some examples, in the compound of Formula (I) R″ is —NCO, and thepresent invention provides a method of making a polyisocyanate. In someexamples, in the compound of Formula (I) R″ is —NCO, and the variables mand n are 1, and the present invention provides a method of making amethod of making a diisocyanate.

An example embodiment of the method of the present invention, whereinthe fused bicyclic polyol is isosorbide, is shown in Scheme 1.

The method can include contacting a fused bicyclic polyol and an acidanhydride to provide a polyacid, such as a diacid. The fused bicyclicpolyol can have the structure:

wherein rings A and B are analogous to rings A and B as described hereinfor Formula (I), except that the ester groups of Formula (I),R″—R′—C(O)O—, are hydroxyl groups, —OH. Thus, as with Formula (I), fusedrings A and B are each independently selected from (C₅-C₁₀)cycloalkyland (C₂-C₁₀)heterocyclyl, m and n are each independently 1-8, and fusedrings A and B are each independently unsubstituted or substituted withat least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J. The variable J independently ateach occurrence is selected from the group consisting of F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

In various embodiments, the polyol can be derived at least in part fromrenewable (e.g., non-petroleum) sources. Advantageously, by deriving thepolyol from renewable sources, the resulting polyisocyanate can be atleast in part derived from renewable sources. For example, in someembodiments the polyol can be isosorbide:

In some embodiments the polyol can be isomannide:

In some embodiments the polyol can be isoidide:

Isosorbide is a natural diol that can be derived from corn. Isosorbide,isomannide, and isoidide are three isomers of 1,4:3,6-dianhydrohexitol,and can be derived from, for example, D-glucose, D-mannose, andL-fructose, respectively. Isosorbide is the most widely available of thethree isomers, as a by-product of the starch industry. Isosorbide,isomannide, and isoidide have characteristics including rigidity,thermal stability, chirality, and lack of toxicity, which makes thesepolyols highly desirable for use in synthesizing environmentally benignand useful polyisocyanates therefrom, and likewise the polyisocyanatesare highly desirable for use in synthesizing environmentally benign anduseful compounds such as polyurethanes.

The acid anhydride can have the structure:

wherein R′ corresponds to R′ in Formula (I). Thus, R′ can be selectedfrom the group consisting of (C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and(C₂-C₁₀)alkynylene. R′ can be unsubstituted, or substituted with atleast one J, as defined herein. In various embodiments, R′ can beethanylene (—CH₂—CH₂—), propanylene (—CH₂—CH₂—CH₂—), or butanylene(—CH₂—CH₂—CH₂—CH₂—). In some examples, the anhydride can be derived atleast in part from renewable sources. Advantageously, by deriving theanhydride from renewable sources, the resulting polyisocyanate can be atleast in part derived from renewable sources; if the polyol is alsorenewably derived, an even larger proportion of the polyisocyanate isrenewably derived. In various embodiments, the anhydride can be succinicanhydride, which can be derived from succinic acid, which can beisolated from, for example, the products of sugar fermentation.

The contacting of the fused bicyclic polyol and the acid anhydride canbe performed under any suitable conditions. In some examples, theanhydride can be used in excess, such as about 1.2 equivalents or less,about 1.4 equivalents, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or about 3.0or more equivalents, with about 1 equivalent of bicyclic polyol. Thereaction can be performed neat, or with any suitable solvent and usingany suitable concentration. The reaction can be stirred or unstirred.The reaction can be cooled, unheated, heated, or any combinationthereof. The reaction can be cooled such that the temperature of thereaction does not exceed about −20° C. or less, about −10° C., −5° C.,0° C., 5° C., 10° C., or about 20° C. or more. The reaction can beunheated. The reaction can be heated to any suitable temperature, forexample, about 80° C. or less, about 90° C., 100, 110, 120, 130, 140,150, 180, 200, 220, 240, 260, 280, or about 300° C. or higher. In someexamples, substantially all of the reaction vessel can be heated, forexample to avoid sublimation of the anhydride. The cooling, no heating,or heating can be performed for any suitable time, for example, about 10min or less, about 30 min, 1 h, 2 h, 4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d,2 d, or about 3 d or more. The resulting polyacid can be carried forwardto the next step crude or can be purified by any suitable technique. Insome examples, the resulting crude polyacid is sufficiently pure suchthat little or no purification is required. In some embodiments, anysolvent can be evaporated using standard techniques such as a rotatingevaporator, and vacuum distillation or chromatography can be used topurify the polyacid.

The contacting of the fused bicyclic polyol and the acid anhydrideprovides a polyacid having the structure of Formula (I):

where Formula (I) is as described herein, wherein R″ is —C(O)OH.

The method also can include contacting the polyacid and an acyl halidegenerator. The acyl halide generator can be any suitable acyl halidegenerator that reacts with a carboxylic acid to generate an acyl halide.For example, the acyl halide generator can be thionyl chloride, thionylbromide, phosphorous pentachloride, phosphorus pentabromide, cyanuricfluoride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorustribromide, phosphorus trichloride, phosphoryl chloride, or any suitablecombination thereof.

Contacting the polyacid and the acyl halide generator can be performedunder any suitable conditions. In some examples, the acyl halidegenerator can be used in excess, such as about 1.2 equivalents or less,about 2 equivalents, 4, 6, 8, 10, 20, 50, 100, or about 500 or moreequivalents, with about 1 equivalent of the polyacid. The reaction canbe performed neat, or with any suitable solvent and at any suitableconcentration. The reaction milieu can include catalytic quantities ofdimethylformamide, such as about 0.001 equivalents or less, or about0.01 equivalents, 0.01-0.1 equivalents, or about 0.1-0.5 equivalents ormore. The reaction can be stirred or unstirred. The reaction can becooled, unheated, heated, or any combination thereof. The reaction canbe cooled to about −20° C. or less, about −10° C., 0° C., 10° C., orabout 20° C. or more. The reaction can be unheated. The reaction can beheated to any suitable temperature, for example, about 30° C. or less,about 40, 50, 60, 70, or about 80° C. or higher. The cooling, noheating, or heating can be performed for any suitable time, for example,about 10 min or less, about 15 min, 20 min, 25 min, 30 min, 40 min, 50min, 1 h, 2 h, 4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d, 2 d, or about 3 d ormore. The resulting polyacyl halide can be isolated in any suitablefashion, or can be carried through to the next step crude. In someembodiments, the crude polyacyl halide is sufficiently pure such thatlittle or no purification is needed. For example, in some embodimentsvacuum distillation or chromatography can be used to purify the polyacylhalide. In some embodiments, any solvent can be evaporated usingstandard techniques such as a rotating evaporator, and distillation canbe used to remove the acyl halide generator from the acyl halide.

The contacting of the polyacid and the acyl halide generator provides apolyacyl halide having the structure of Formula (I) wherein R″ is —C(O)Xwherein X is halide. For example, the polyacyl halide can be a polyacylchloride, or a diacyl chloride.

The method can include contacting the polyacyl halide and an azidegenerator. The azide generator can be any suitable azide generator thatreacts with an acyl halide to generate an acyl azide, such as anysuitable salt of an azide ion (N₃ ⁻). For example, the azide generatorcan be sodium azide, trimethylsilyl azide, triethylsilyl azide, lithiumazide, potassium azide, tetrabutylammonium azide,tert-butyldimethylsilyl azide, tert-butyldiphenylsilyl azide, or anysuitable combination thereof. The contacting of the polyacid halide andan azide generator can provide a polyacyl azide having the structure ofFormula (I) wherein R″ is —C(O)N₃. The polyacyl azide can undergo aCurtius rearrangement to provide a polyisocyanate having the structureof Formula (I) wherein R″ is —NCO; thus, the contacting of the polyacidhalide and the azide generator under suitable conditions can provide apolyisocyanate having the structure of Formula (I) wherein R″ is —NCO,such as a diisocyanate. The Curtius rearrangement can occur in aseparate step from the contacting of the polyacid halide and the azidegenerator, or the Curtius rearrangement can occur in the same step.

Contacting the polyacyl halide and an azide generator can be performedunder any suitable conditions. For example, in embodiments in which thepolyacyl azide is generated and a discrete step is used to elicit theCurtius rearrangement and generate the polyisocyanate, the contacting ofthe polyacyl halide and the azide generator can occur in any suitablefashion. For example, the acyl azide generator can be used in excess,such as about 1.2 equivalents or less, about 2 equivalents, 3, 4, 5, 6,7, 8, 10, 20, or about 30 or more equivalents, with about 1 equivalentof the polyacyl halide. The acyl azide generator can be used in anaqueous solution. The reaction can be performed neat, or with anysuitable solvent, such as toluene, using any suitable concentration. Thereaction can be stirred or unstirred. The reaction can be cooled,unheated, heated, or any combination thereof. The reaction can be cooledsuch that the temperature of the reaction does not exceed about −20° C.or less, about −10° C., −5° C., 0° C., 1° C., 2° C., 3° C., 4° C., 5°C., 10° C., or about 20° C. or more. The reaction can be unheated. Thereaction can be heated to any suitable temperature, for example, about30° C. or less, about 40° C., 60° C., 80° C., 100° C., or about 110° C.or higher. The cooling, no heating, or heating can be performed for anysuitable time, for example, about 10 min or less, or about 15 min, 20min, 25 min, 30 min, 40 min, 50 min, 1 h, 2 h, 4 h, 6 h, 12 h, 18 h, 24h, 1.5 d, 2 d, or about 3 d or more. The resulting azide can be workedup in any suitable fashion, for example by removing any aqueous phase,recovering any organic material from the aqueous phase, washing theorganic phase with at least one of aqueous base, water, and brine, anddrying the organic phase. In various embodiments, the resulting azide isnot isolated any further than as a worked up organic solution, due atleast in part to the explosion risk of organic azides in a concentratedstate.

In embodiments in which the polyacyl azide is generated and a discretestep is used to elicit the Curtius rearrangement and generate thepolyisocyanate, the polyacyl azide can be treated in any suitablefashion to generate the polyisocyanate. In various embodiments, thepolyacyl azide can be added neat or as a solution, for example as asolution in toluene, to a solvent, such as refluxing toluene. Thepolyacyl azide can be added to the solvent at any rate, for example ator less than a rate sufficient to approximately maintain steadyrefluxing of the solvent and steady release of nitrogen gas but not sofast as to generate nitrogen at a rate that is uncontrolled and not sofast as to cause uncontrolled boiling of the solvent. The reaction canbe stirred or unstirred. Prior to and during addition of the polyacylazide to the solvent, the reaction can be heated or maintained at anysuitable temperature, for example, about 30° C. or less, about 40, 60,80, 100, or about 110° C. or higher. Once the addition of the polyacylazide is complete, the reaction can be complete, or the reaction can beallowed to continue for any suitable amount of time. In someembodiments, once the addition of the polyacyl azide is complete, thereaction is heated or maintained at any suitable temperature, such asabout reflux temperature, for any suitable amount of time, for example,about 5 min or less, or about 10 min, about 15 min, 20 min, 25 min, 30min, 40 min, 50 min, 1 h, 2 h, 4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d, 2 d,or about 3 d or more. The resulting polyisocyanate can be purified inany suitable fashion. In some embodiments, the crude polyisocyanate issufficiently pure such that little or no purification is needed. In someexamples, any solvent can be evaporated using standard techniques suchas a rotating evaporator, and the polyisocyanate can be purified usingvacuum distillation or chromatography.

In examples in which the polyacyl azide is generated but thepolyisocyanate is generated in a single step, contacting the polyacylhalide and the azide generator can occur in any suitable fashion. Insome examples, the azide generator can be used in excess, such as about1.2 equivalents or less, about 2 equivalents, 4, 6, 8, 10, 20, or about30 or more equivalents, with about 1 equivalent of the polyacyl halide.The reaction can be performed neat, or with any suitable solvent. Insome examples, the azide generator can be added neat or in a solutionhaving a suitable concentration to the polyacyl halide. The addition canbe performed at a rate sufficient that the nitrogen gas evolution thatoccurs is controlled, and such that the temperature is maintained at orbelow about 50° C., or about 60° C., 70° C., 80° C., 90° C., 100° C.,110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., or about180° C. or above. In various embodiments, the reaction milieu caninclude suitable concentrations of a phase transfer catalyst, such as atetra(C₁₋₁₀)alkylammonium halide salt (e.g. when using sodium azide asthe azide generator), alkaloid-derived phase transfer catalysts, orphosphonium salts; in other embodiments, no phase transfer catalyst ispresent.

In some embodiments, In some embodiments, a silicon-based reagent can beused such as trimethylsilyl chloride, trimethylsilyl triflate, ortri(C₁₋₂₀alkyl)silyl halide, or the analogous germanium- or tin-basedreagent can be used (e.g. tetra(C₁₋₂₀ alkyl)germanium halide ortri(C₁₋₂₀ alkyl)germanium halide)); in other embodiments, nosilicon-based, germanium-based, or tin-based reagent is used. Once theaddition is complete, the reaction can be maintained at the temperatureused during the addition of the azide generator or at a differenttemperature for any suitable duration, for example, about 10 min orless, or about 15 min, 20 min, 25 min, 30 min, 40 min, 50 min, 1 h, 2 h,4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d, 2 d, or about 3 d or more. Theresulting polyisocyanate can be purified in any suitable fashion. Insome embodiments, the crude polyisocyanate is sufficiently pure suchthat little or no purification is needed. In some examples, any solventcan be evaporated using standard techniques such as a rotatingevaporator, and the polyisocyanate can be purified using vacuumdistillation or chromatography.

In some examples, the polyacid is contacted with suitable reagents undersuitable conditions to undergo a Schmidt reaction to directly yield thepolyacyl azide or polyisocyanate. Reagents and conditions suitable forelicitation of a Schmidt reaction are readily known to one of ordinaryskill in the art, for example hydroazoic acid can be contacted with thepolyacid with expulsion of nitrogen to give the polyisocyanate.

Polyurethane.

In various embodiments, the present invention provides a polyurethanederived from any suitable compound of Formula (I). In some examples, acompound having the structure of Formula (I) where R″=—NCO can besynthesized from any of the compounds of Formula (I) having R″=—C(O)OH,—C(O)O⁻X⁺, —C(O)F, —C(O)Cl, —C(O)Br, —C(O)I, —C(O)N₃ by using anembodiment of the method of the present invention or by using anothermethod. The compound of Formula (I) with R″=—NCO, either made using thepolyacid, polyacid salt, polyacyl halide, or polyacyl azide, orsynthesized via a different route, can be combined with any one or moresuitable alcohols to cause a polymerization reaction between thehydroxyl moieties of the alcohol and the isocyanate moieties of thepolyisocyanate to create a polyurethane. The polyurethanes of thepresent invention include any polyurethane that is a reaction product ofat least a compound of Formula (I) having R″=—NCO and an alcohol, suchas a polyol, chain extender, and the like. Thus, the polyurethanes ofthe present invention include a plurality of subunits having thestructure of Formula (II):

For a polyurethane to include a plurality of subunits having thestructure of Formula (II), the structure of Formula (II) occurs at leasttwice in the polyurethane molecule. The polyurethane including aplurality of subunits of Formula (II) can be derived from a suitablecompound of Formula (I); therefore, various aspects of Formula (II) havethe equivalent features as described herein for Formula (I). However,the polyurethane including Formula (II) can be derived from any suitablecompound, and the method of derivation is not restricted to compounds ofFormula (I).

Formula (II) includes fused rings A and B, which share a singlecarbon-carbon bond. Rings A and B can be the same or different, and areeach independently selected from (C₅-C₁₀)cycloalkyl and(C₂-C₁₀)heterocyclyl, wherein the designated number of carbon atomsincludes the two carbon atoms that are shared by rings A and B. In someexamples, rings A and B can be the same size, and can both becyclopentyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclononyl, orcyclodecyl. The hydrogen atom attached to each shared carbon atom canhave any suitable stereochemical configuration with respect to eachother and with respect to other functional groups on rings A and B, andcan be syn or anti.

Rings A and B can have any suitable number and variety of functionalgroups thereon. Rings A and B each include one or more estersubstituents having the formula —C(O)—NH—R′—C(O)O—. The one or moreester substitutents have an ester moiety at the point of attachment tofused rings A and B, and can have a carbamate moiety at the other endthat can be formed from the reaction of an —OH group of the one or morealcohols used to synthesize the polyurethane and an —NCO group of thepolyisocyanate of Formula (I) wherein R″ is —NCO. The variables m and nare each independently 1-8; thus, Rings A and B can each independentlyhave about 1 to 8 ester substituents thereon. The variables m and n canhave different values, or the variable m and n can be equal. Thevariables m and n can each be 1. Rings A and B can each have the sametype and number of ester substituents or a different type and number ofester substituents. Rings A and B each have at least one estersubstituent. In some examples, fused rings A and B can be eachindependently unsubstituted with the exception of the estersubstituents.

In some examples, fused rings A and B can be each independentlysubstituted with at least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl,(C₂-C₁₀)alkynyl, (C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J. The variable J independently ateach occurrence is selected from the group consisting of F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

In Formula (II), the variable R′ in the ester substituent is selectedfrom the group consisting of (C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and(C₂-C₁₀)alkynylene. In some examples, R′ can be unsubstituted, and inother examples, R′ can be substituted with at least one J, as definedherein. In various examples, R′ can be ethanylene (—CH₂—CH₂—),propanylene (—CH₂—CH₂—CH₂—), or butanylene (—CH₂—CH₂—CH₂—CH₂—).

In some embodiments, at least one of the ester substituents having theformula —C(O)—NH—R′—C(O)O— is alpha to a carbon atom shared by rings Aand B, for example, the ester substituent can be substituted on an atomof ring A or B that is bound to a carbon atom shared by rings A and B.In some examples, at least one of the one or more ester substituents oneach of rings A and B is alpha to a carbon atom shared by rings A and B.In some examples, at least one of the one or more ester substituents onring A is alpha to a carbon atom shared by rings A and B, and at leastone of the ester substituents on ring B is alpha to the other carbonatom shared by rings A and B, and m can equal n or both m and n can be1.

In some examples, at least one of rings A and B include at least oneoxygen atom. In some embodiments, each of rings A and B include at leastone oxygen atom. In some examples, each of rings A and B is atetrahydrofuran ring (e.g. cyclotetramethylene oxide, having anysuitable substituents), where each of the two carbon atoms shared byrings A and B is alpha to the oxygen atom in at least one of rings A andB. In some examples, each of rings A and B is a tetrahydrofuran ring,where one the two carbon atoms shared by rings A and B is alpha to theoxygen atom in ring A, and the other carbon atom shared by rings A and Bis alpha to the oxygen atom in ring B.

In some embodiments, m and n are 1, and each of rings A and B includesat least one oxygen atom, such that one the two carbon atoms shared byrings A and B is alpha to the at least one oxygen atom in ring A andalpha to the ester substituent on ring B, and the other carbon atomshared by rings A and B is alpha to the at least one oxygen atom in ringB and alpha to the ester substituent on ring A.

In various embodiments, the subunit having the structure of Formula (II)can be:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from suitable fusedbicyclic diols and a suitable cyclic anhydride using various methods ofthe present invention.

In various embodiments, the subunit having the structure of Formula (II)can be:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from suitable fusedbicyclic diols and succinic anhydride using various methods of thepresent invention.

In various embodiments, the subunit having the structure of Formula (II)has a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isosorbide ring system, having the structure:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from isosorbide and asuitable anhydride using various methods of the present invention.

In various embodiments, the compound of Formula (II) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isosorbide ring system, where R′ is ethanylene,having the structure:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from isosorbide andsuccinic anhydride using various methods of the present invention.

In various embodiments, the compound of Formula (II) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isomannide ring system, having the structure:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from isomannide and asuitable cyclic anhydride using various methods of the presentinvention.

In various embodiments, the compound of Formula (II) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isomannide ring system, where R′ is ethanylene,having the structure:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from isomannide andsuccinic anhydride using various methods of the present invention.

In various embodiments, the compound of Formula (II) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isoidide ring system, having the structure:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from isoidide and asuitable cyclic anhydride using various methods of the presentinvention.

In various embodiments, the compound of Formula (II) is a diisocyanatehaving a fused bicyclic tetrahydrofuran ring system with thestereochemistry of an isoidide ring system, where R′ is ethanylene,having the structure:

In some examples, a polyurethane including a plurality of this subunitcan be derived from diisocyanates provided by various embodiments of thepresent invention, which in turn can be derived from isoidide andsuccinic anhydride using various methods of the present invention.

Alcohols that can be contacted with polyisocyanates to generate thepolyurethanes of the present invention include any suitable alcohol. Inone example, the alcohol is a polyol. In some examples, the polyol canbe isosorbide, isomannide, isoidide, or any combination thereof.Advantageously, by using a polyol that is renewably derived incombination with a polyisocyanate that is at least in part renewablyderived, the resulting polyurethane can be derived in greater proportionfrom renewable materials. For example, the polyol can be one polyol, ora mixture of different polyols. In some examples, the polyol can besorbitol or glycerine. The polyol can be a polyester polyol, a polyetherpolyol, or any combination thereof. Polyether polyols can include anypoly(C₁₋₁₀ hydrocarbylene oxide), wherein the hydrocabylene group caninclude any alkylene, alkenylene, alkynylene, arylene, or cycloalkylenegroup, wherein the hydrocarbylene can optionally be substituted with anysuitable organic group, halide, or hydroxyl group. Examples ofpolyethers can include polyethylene glycol, polypropylene glycol,polybutylene glycol, dipropylene glycol, diethylene glycol, or sucrose.For example, polyether polyols can include any polyether polyol derivedfrom esterification of a (C₂₋₂₀)diacid and a glycol or polyol, or anypolyether polyol derived from transesterification ofpoly(ethyleneterephthalate) or dimethylterepthalate with a glycol orpolyol.

In addition to the polyisocyanate and the alcohol, the polyurethanes ofthe present invention can derived from mixtures that include any othersuitable ingredient, such as, for example, chain extenders, crosslinkers, catalysts, surfactants, other isocyanates, stabilizers,lubricants, dyes, pigments, inorganic and/or organic fillers, andreinforcing materials such as impact modifiers.

The chain extender, if present, can be any suitable chain extender. Forexample, the chain extender can be 1,4-butanediol, 1,6-hexanediol,1,8-octandiol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol,1,4-cyclohexanedimethanol, p-xylene glycol, and1,4-bis(2-hydroxyethoxy)benzene.

Other polyisocyanates can include any suitable polyisocyanate. Forexample, the other polyisocyanate can be 4,4′-methylenediphenyldiisocyanate (MDI), methylene bis(cyclohexyl)diisocyanate (H12MDI),p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1,4-diisocyanate(CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylenediisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI),p-tetramethylxylene diisocyanate (p-TMXDI), m-tetramethylxylenediisocyanate (m-TMXDI), isomers thereof, and combinations thereof.

The polyurethanes of the present invention are easily adaptable to avariety of fabrication techniques including solvent casting, blowmolding, machining to various shapes and other conventional processingtechniques such as injection molding and extrusion.

The polyurethanes of the present invention can have any suitable rangeof molecular weight. For example, the polyurethane can have a molecularweight of about 5000 to about 1,000,000, or about 2500 to 10,000,000.

The present invention provides any solution or dispersion of apolyurethane of the present invention. Such a dispersion can include anaqueous liquid having any suitable proportion of polyurethane therein.The dispersion can include about 50% water or less, about 60% water,70%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.9%,or 99.99% water, or more, by mass. The dispersion can include about 50%of the polyurethane or more, or about 40% polyurethane, 30%, 20%, 15%,10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.1%, 0.01%, 0.001%, 0.0001%,or about 0.00001% or less polyurethane by mass. The aqueous dispersioncan include any other suitable component, or substantially no othercomponent other than water and polyurethane.

Embodiments of the present invention encompass any suitable method ofgenerating polyurethanes from the compounds of Formula (I), for exampleby contacting a compound of Formula (I) having R″=—NCO with any suitablealcohol under conditions sufficient to generate a polyurethane. Theconditions can be any suitable conditions. The reaction can be neat orcan include a solvent with any suitable concentration of reactants. Thereaction can include a catalyst, or the reaction can include nocatalyst. In addition to the polyisocyanate and the alcohol, thereaction can include any other suitable ingredient, such as, forexample, chain extenders, cross linkers, catalysts, surfactants, orother isocyanates. The reaction can be cooled, not heated, heated, orany combination thereof. The reaction can be cooled such that thetemperature of the reaction does not exceed about −20° C. or less, about−10° C., −5° C., 0° C., 5° C., 10° C., or about 20° C. or more. Thereaction can be unheated. The reaction can be heated to any suitabletemperature, for example, about 80° C. or less, about 90° C., 100, 110,120, 130, 140, 150, 180, 200, 220, 240, 260, 280, or about 300° C. orhigher. The cooling, no heating, or heating can be performed for anysuitable time, for example, about 10 min or less, about 30 min, 1 h, 2h, 4 h, 6 h, 12 h, 18 h, 24 h, 1.5 d, 2 d, or about 3 d or more. Anysuitable work up or purification procedure can be used. In someexamples, the crude polyurethane is sufficiently pure such thatadditional purification is not needed.

Examples

The present invention can be better understood by reference to thefollowing examples which are offered by way of illustration. The presentinvention is not limited to the examples given herein.

General. All reactions were performed with magnetic stirring. Allnon-aqueous reactions were performed under an argon atmosphere.HPLC-grade toluene and reagents of the most economical grade were usedas received. Reactions were monitored by ¹H NMR spectroscopy on BrukerDRX-400 or DRX-600 instruments. NMR spectra were calibrated usingresidual undeuterated solvent as an internal reference. ¹H NMRmultiplicities refer to apparent multiplicities as determined visually:s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, b=broad.Thin-layer chromatography was carried out on Grace Davison Davisilsilica gel plates (0.25 mm thickness, with fluorescent indicator).

Isosorbide-Based Diisocyanate Example 1 Synthesis of Diacid 3

As illustrated in Scheme 2, diacid 3 was synthesized from isosorbide 1and succinic anhydride 2.

A mixture of isosorbide (1, 7.31 g, 50 mmol) and succinic anhydride (2,11.51 g, 115 mmol, 2.3 equiv) was heated at 120° C. for 24 hr to givediacid 3 as a viscous orange oil. To avoid sublimation of succinicanhydride 2, the entire reaction vessel was heated. The chemical yieldwas estimated by ¹H NMR analysis to be approximately 100%. Sublimationof succinic anhydride (2) from the crude material afforded a sample ofdiacid 3 for analysis. 3: R_(f)=0.43 (silica gel, EtOAc); [α]_(D)²³=+90.9° (c=1.00, CHCl₃); IR (thin film): ν_(max)=1739, 1716 cm⁻¹; ¹HNMR (400 MHz, CDCl₃): δ=10.51 (br, 2H), 5.21 (s, 1H), 5.17 (q, J=5.4 Hz,1H), 4.83 (t, J=5.1 Hz, 1H), 4.47 (d, J=4.7, 1H), 3.94 (m, 3H), 3.81(dd, J=10.0, 5.1 Hz, 1H), 2.69 (s, 4H), 2.65 (m, 4H); ¹³C NMR (100 MHz,CDCl₃): δ=178.01, 177.95, 171.71, 171.33, 85.88, 80.87, 78.37, 74.42,73.33, 70.54, 29.04, 29.01, 28.98, 28.76 ppm; HRMS (ESI-QTOF) calcd forC₁₄H₁₇O⁺ [M−H⁺]: 345.0822. found: 345.0827.

Example 2 Synthesis of Diacid Chloride 4

As illustrated in Scheme 3, diacid chloride 4 was synthesized fromdiacid 3.

To a solution of crude diacid 3 (50 mmol) in thionyl chloride (100 mL)at 0° C. was added dimethylformamide (0.05 mL, 0.5 mmol, 0.01 equiv).Vigorous gas evolution was observed for approximately 30 min. Afteranother 1.5 hr, excess thionyl chloride was distilled out under reducedpressure (30° C.) to give diacid chloride 4 as an orange oil. Thechemical yield was estimated by ¹H NMR analysis to be approximately 85%.A sample of diacid chloride 4 for analysis was obtained by the reactionof a purified sample of diacid 3. 4: R_(f)=0.35 (silica gel, EtOAc);[α]_(D) ²³=+49.0° (c=1.00, CHCl₃); IR (thin film) ν_(max)=1794, 1747cm⁻¹; ¹H NMR (400 MHz, CDCl₃): δ=5.23 (d, J=3.1 Hz, 1H), 5.18 (q, J=5.4Hz, 1H), 4.84 (t, J=5.1 Hz, 1H), 4.47 (d, J=4.7 Hz, 1H), 3.94 (m, 3H),3.83 (dd, J=10.1, 4.9 Hz, 1H), 3.23 (m, 4H), 2.74 (td, J=6.6, 2.9 Hz,2H), 2.69 (t, J=6.4 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ=173.11, 173.02,170.45, 170.15, 85.89, 80.83, 78.68, 74.70, 73.28, 70.58, 41.76, 41.68,29.40, 29.14 ppm.

Example 3 Synthesis of Diacyl Azide 5

As illustrated in Scheme 4, diacyl azide 5 was synthesized from diacidchloride 4.

A solution of crude diacid chloride 4 (50 mmol) in toluene (125 mL) wasadded dropwise over the course of 40 min to an aqueous solution ofsodium azide (16.25 g, 250 mmol, 5 equiv) at 0° C. The rate of additionwas controlled so that the internal temperature of the reaction did notexceed 3° C. The reaction was continued at 0° C. for 20 min aftercomplete addition. The reaction mixture was partitioned into two phases,and the organic phase was washed with 1×100 mL 10% potassium carbonatesolution, 1×100 mL water, and 2×100 mL brine, then dried over Na₂SO₄.Diacyl azide 5 was not concentrated due to its instability in pure form.The chemical yield of diacyl azide 5 from isosorbide (1) was estimatedby ¹H NMR analysis of the crude material using EtOAc as an internalstandard to be approximately 85%. 5: R_(f)=0.60 (silica gel, EtOAc); IR(PhMe) ν_(max)=2138, 1746, 1721 cm¹; ¹H NMR (400 MHz, CDCl₃ containing<5% PhMe and <1% EtOAc): δ=5.70 (d, J=3.3 Hz, 1H), 5.52 (q, J=5.3 Hz,1H), 5.22 (t, J=5.1 Hz, 1H), 4.86 (d, J=4.7 Hz, 1H), 4.42 (m, 2H), 4.24(d, J=5.3 Hz, 2H), 3.08-2.90 (m, 8H).

Example 4 Synthesis of Diisocyanate 6

As illustrated in Scheme 5, diisocyanate 6 was synthesized from diacylazide 5.

A toluene solution of diacyl azide 5 (50 mmol, toluene recovered fromExample 3) was added dropwise over the course of 45 min to 10 mL oftoluene at 110° C. The rate of addition was controlled so that a steadyreflux rate and steady gas formation were achieved. The reaction wascontinued for 15 min after complete addition. Concentration underreduced pressure gave crude diisocyanate 6 as a dark orange oil.Diisocyanate 6 was purified by distillation (186-189° C., 54 mTorr) togive a light orange oil [10.19 g, 60% overall yield from isosorbide(1)]. 6: R_(f)=0.70 (silica gel, EtOAc); [α]_(D) ²³=+69.0° (c=1.00,CHCl₃); IR (thin film) ν_(max)=2274, 1747 cm⁻¹; ¹H NMR (600 MHz, CDCl₃):δ=5.26 (d, J=3.1 Hz, 1H), 5.21 (q, J=5.5 Hz, 1H), 4.87 (t, J=5.1 Hz,1H), 4.50 (d, J=4.7 Hz, 1H), 3.97 (m, 3H), 3.85 (dd, J=10.1, 5.0 Hz,1H), 3.60 (m, 4H), 2.67 (t, J=6.4 Hz, 2H), 2.62 (t, J=6.4 Hz, 2H); ¹³CNMR (150 MHz, CDCl₃): δ=170.18, 169.90, 123.40, 123.30, 85.97, 80.81,78.54, 74.57, 73.35, 70.55, 38.67, 38.65, 35.69, 35.46 ppm; HRMS(ESI-QTOF) calcd for C₁₄H₁₇N₂O₈ ⁺[M+H]: 341.0985. found: 341.0979.

Example 5 Synthesis of Diisocyanate 6

As illustrated in Scheme 6, diisocyanate 6 was synthesized from diacidchloride 4.

Trimethylsilyl azide (4.0 mL, 30 mmol, 6 equiv) was added dropwise todiacid chloride 4 (1.92 g, 5 mmol) at 140° C., resulting in vigorous gasevolution. The reaction was continued at 140° C. for 30 min aftercomplete addition. Concentration under reduced pressure gave crudediisocyanate 6 as a dark red oil. The chemical yield of diisocyanate 6from isosorbide (1) was estimated by ¹H NMR analysis to be approximately50%.

Isomannide-Derived Diisocyanate Example 6 Synthesis of Diacid 8

As illustrated in Scheme 7, diacid 8 was synthesized from isomannide 7and succinic anhydride 2.

A mixture of isomannide (7, 7.31 g, 50 mmol, 1 equiv) and succinicanhydride (2, 11.51 g, 115 mmol, 2.3 equiv) was heated at 120° C. for 24hr to give diacid 8 as a viscous orange oil. To avoid sublimation ofsuccinic anhydride 2, the entire reaction vessel was heated. Vacuumsublimation of succinic anhydride (2) from the crude material affords asample of diacid 8 for analysis. 8: R_(f)=0.38 (silica gel, EtOAc);[α]_(D) ²³=+116.9 (c=1.00, CHCl₃); IR (thin film): ν_(max)=1741, 1717cm⁻¹; ¹H NMR (400 MHz, CDCl₃): δ=8.29 (br, 2H), 5.10 (d, J=5.8 Hz, 2H),4.68 (dd, J=9.3, 3.8 Hz, 2H), 4.01 (dd, J=9.6, 6.1 Hz, 2H), 3.79 (dd,J=9.6, 6.3 Hz, 2H), 2.77-2.70 (m, 4H), 2.70-2.65 (m, 4H) ppm; ¹³C NMR(100 MHz, CDCl₃): δ=178.20, 171.37, 80.58, 73.98, 70.72, 29.40, 29.25ppm; HRMS (ESI-QTOF) calcd for C₁₄H₁₇O₁₀ ⁻ [M−H⁺]: 345.0822. found:345.0821; DSC (He, 10° C. min⁻¹): T_(g)=−2° C.

Example 7 Synthesis of Diacid Chloride 9

As illustrated in Scheme 8, diacid chloride 9 was synthesized fromdiacid 8.

To a solution of crude diacid 8 (1 equiv) in thionyl chloride at 0° C.was added dimethylformamide (0.01 equiv). Vigorous gas evolution wasobserved for approximately 30 min. After another 1.5 hr, excess thionylchloride was distilled out under reduced pressure (30° C.) to givediacid chloride 9. The chemical yield was estimated by ¹H NMR analysis.A sample of diacid chloride 9 for analysis was obtained by the reactionof a purified sample of diacid 8. 9: ¹H NMR (400 MHz, CDCl₃):δ=5.13-5.06 (m, 2H), 4.70-4.65 (m, 2H), 4.03 (dd, J=9.4, 6.3 Hz, 2H),3.80 (dd, J=9.4, 6.6 Hz, 2H), 3.23 (td, J=6.5, 4.0 Hz, 4H), 2.78-2.72(m, 4H) ppm; ¹³C NMR (100 MHz, CDCl₃): δ=178.20, 171.37, 80.58, 73.98,70.72, 29.40, 29.25 ppm.

Example 8 Synthesis of Diacyl Azide 10

As illustrated in Scheme 9, diacyl azide 10 was synthesized from diacidchloride 9.

A solution of crude diacid chloride 9 (50 mmol, 1 equiv) in toluene wasadded dropwise to an aqueous solution of sodium azide (16.25 g, 250mmol, 5 equiv) at 0° C. The rate of addition was controlled so that theinternal temperature of the reaction did not exceed 3° C. The reactionwas continued at 0° C. for 20 min after complete addition. The reactionmixture was partitioned into two phases, and the organic phase waswashed once with 100 mL 10% potassium carbonate solution, once with 100mL water, and twice with 100 mL brine, then dried over Na₂SO₄. Diacylazide 10 was not concentrated due to its instability in pure form. Thechemical yield of diacyl azide 10 from isomannide (7) was estimated by¹H NMR analysis of the crude material. 10: ¹H NMR (400 MHz, CDCl₃):δ=5.32-5.23 (m, 2H), 4.88-4.81 (m, 2H), 4.21 (dd, J=9.5, 6.5 Hz, 2H),4.01 (dd, J=9.5, 6.7 Hz, 2H), 2.94-2.79 (m, 8H) ppm.

Example 9 Synthesis of Diisocyanate 11

As illustrated in Scheme 10, diisocyanate 11 was synthesized from diacylazide 10.

A toluene solution of diacyl azide 10 (50 mmol, with toluene recoveredfrom Example 8) was added dropwise to toluene at 110° C. The rate ofaddition is controlled so that a steady reflux rate and steady gasformation were achieved. The reaction was continued for 15 min aftercomplete addition. Concentration under reduced pressure gave crudediisocyanate 11 as a dark orange oil. Diisocyanate 11 was purified bydistillation (197-199° C., 230 mTorr) to give a light orange oil. 11:R_(f)=0.81 (silica, EtOAc); [α]_(D) ²³=+155.9 cm³ g⁻¹ dm⁻¹ (c=1.00 gcm⁻³, CHCl₃); IR (thin film): ν_(max)=2278, 1738 cm⁻¹; ¹H NMR (400 MHz,CDCl₃): δ=5.18-5.11 (m, 2H), 4.74-4.71 (m, 2H), 4.06 (dd, J=9.5, 6.4 Hz,2H), 3.83 (dd, J=9.5, 6.7 Hz, 2H), 3.62 (td, J=6.3, 3.1 Hz, 4H), 2.68(t, J=6.3 Hz, 4H) ppm; ¹³C NMR (100 MHz, CDCl₃): δ=170.20, 123.27,80.39, 74.27, 70.47, 38.67, 35.43 ppm; HRMS (ESI-QTOF) calcd forC₁₄H₁₆N₂ONa⁺ [M+Na⁺]: 363.0804. found: 363.0792.

Example 10 (Hypothetical) Synthesis of Diisocyanate 11

As illustrated in Scheme 11, diisocyanate 11 is synthesized from diacidchloride 9.

Trimethylsilyl azide (6 equiv) is added dropwise to diacid chloride 9(1.92 g, 5 mmol) at 140° C., resulting in vigorous gas evolution. Thereaction is continued at 140° C. for 30 min after complete addition.Concentration under reduced pressure gives crude diisocyanate 11 as adark red oil. The chemical yield of diisocyanate 11 from isomannide (7)is estimated by ¹H NMR analysis.

Isoidide-Derived Diisocyanate Example 11 (Hypothetical) Synthesis ofDiacid 13

As illustrated in Scheme 12, diacid 13 is synthesized from isoidide 12and succinic anhydride 2.

A mixture of isoidide (12, 1 equiv) and succinic anhydride (2, 2.3equiv) is heated at 120° C. for 24 hr to give diacid 13. To avoidsublimation of succinic anhydride 2, the entire reaction vessel can beheated. The chemical yield is estimated by ¹H NMR analysis. Sublimationof succinic anhydride (2) from the crude material affords a sample ofdiacid 13 for analysis.

Example 12 (Hypothetical) Synthesis of Diacid Chloride 14

As illustrated in Scheme 13, diacid chloride 14 is synthesized fromdiacid 13.

To a solution of crude diacid 13 (1 equiv) in thionyl chloride at 0° C.is added dimethylformamide (0.01 equiv). Vigorous gas evolution isobserved for approximately 30 min. After another 1.5 hr, excess thionylchloride is distilled out under reduced pressure (30° C.) to give diacidchloride 14. The chemical yield is estimated by ¹H NMR analysis. Asample of diacid chloride 14 for analysis is obtained by the reaction ofa purified sample of diacid 13.

Example 13 (Hypothetical) Synthesis of Diacyl Azide 15

As illustrated in Scheme 14, diacyl azide 15 is synthesized from diacidchloride 14.

A solution of crude diacid chloride 14 (1 equiv) in toluene is addeddropwise to an aqueous solution of sodium azide (5 equiv) at 0° C. Therate of addition is controlled so that the internal temperature of thereaction does not exceed 3° C. The reaction is continued at 0° C. for 20min after complete addition. The reaction mixture is partitioned intotwo phases, and the organic phase is washed once with 10% potassiumcarbonate solution, once with water, and twice with brine, then driedover Na₂SO₄. Diacyl azide 15 is not concentrated due to its instabilityin pure form. The chemical yield of diacyl azide 15 from isoidide (12)is estimated by ¹H NMR analysis of the crude material.

Example 14 (Hypothetical) Synthesis of Diisocyanate 16

As illustrated in Scheme 15, diisocyanate 16 is synthesized from diacylazide 15.

A toluene solution of diacyl azide 15 (with toluene recovered fromExample 13) is added dropwise to toluene at 110° C. The rate of additionis controlled so that a steady reflux rate and steady gas formation areachieved. The reaction is continued for 15 min after complete addition.Concentration under reduced pressure gives crude diisocyanate 16 as adark orange oil. Diisocyanate 16 is purified by distillation to give alight orange oil.

Example 15 (Hypothetical) Synthesis of Diisocyanate 16

As illustrated in Scheme 16, diisocyanate 16 is synthesized from diacidchloride 14.

Trimethylsilyl azide (6 equiv) is added dropwise to diacid chloride 14(1.92 g, 5 mmol) at 140° C., resulting in vigorous gas evolution. Thereaction is continued at 140° C. for 30 min after complete addition.Concentration under reduced pressure gives crude diisocyanate 16 as adark red oil. The chemical yield of diisocyanate 16 from isoidide (12)is estimated by ¹H NMR analysis.

Synthesis of Polyurethanes Example 16 Synthesis of Polyurethane

As illustrated in Scheme 17, polyurethane 18a was synthesized from diol1 and diisocyanate 6.

Diisocyanate 6 (1.52 g, 4.45 mmol), isosorbide (1, 620 mg, 4.24 mmol)and DMF (4 mL) were stirred over activated and powdered 4 Å molecularsieves for 30 min. Dibutyl tin laurate (DBTDL, ca. 10 μL) was added, andthe reaction mixture was heated at 120° C. for 18 hr. The reaction wasfiltered into methanol (50 mL), and the resultant white precipitate wascollected. Polyurethane 18a was dried at 50° C. under reduced pressureto yield an orange solid (1.08 g, 52.4% yield). 7: DSC (10° C./min):T_(g)=63.9° C., T_(m)=123.2° C., T_(d)=215.0 OC; GPC (DMF): Mn=5,147 gmol⁻¹, M_(w)=9,177 g mol⁻¹, M_(w)/Mn=1.78; TGA: T_(d)=200° C.

Example 17 (Hypothetical) Synthesis of Polyurethanes

As illustrated in Scheme 18 and Table 1, diisocyanates 6, 11, 16 areused to synthesize polyurethanes 18a-d, 19a-d, and 20a-d using polyols1, 7, 12, or 17.

TABLE 1 Reactions performed in Scheme 18. Polyol DiisocyanatePolyurethane 1 6 18a 7 6 18b 12 6 18c 17 6 18d 1 11 19a 7 11 19b 12 1119c 17 11 19d 1 16 20a 7 16 20b 12 16 20c 17 16 20d

The terms and expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention that in theuse of such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments and optional features, modification and variation of theconcepts herein disclosed may be resorted to by those of ordinary skillin the art, and that such modifications and variations are considered tobe within the scope of this invention as defined by the appended claims.

Additional Embodiments

The present invention provides for the following exemplary embodiments,the numbering of which is not to be construed as designating levels ofimportance:

Embodiment 1 provides a compound of Formula (I):

wherein fused rings A and B are each independently selected from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl; m and n are eachindependently 1-8; R′ is selected from the group consisting of(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and (C₂-C₁₀)alkynylene, whereinR′ is unsubstituted or substituted with at least one J; R″ is selectedfrom the group consisting of —C(O)OH, —C(O)O⁺X⁺, —C(O)F, —C(O)Cl,—C(O)Br, —C(O)I, —C(O)N₃, and —NCO, wherein X⁺ is a counterion; fusedrings A and B are each independently unsubstituted or substituted withat least one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and wherein J independently ateach occurrence is selected from the group consisting of F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

Embodiment 2 provides the compound of Embodiment 1, wherein R″ is —NCO.

Embodiment 3 provides the compound of any one of Embodiments 1-2,wherein R′ is unsubstituted.

Embodiment 4 provides the compound of any one of Embodiments 1-3,wherein R′ is —CH₂—CH₂—.

Embodiment 5 provides the compound of any one of Embodiments 1-4,wherein rings A and B are unsubstituted with the exception of the estersubstituents including R′ and R″.

Embodiment 6 provides the compound of any one of Embodiments 1-5,wherein m=n=1, and one of the ester substituents including R′ and R″ isalpha to at least one carbon atom shared by rings A and B.

Embodiment 7 provides the compound of any one of Embodiments 1-6,wherein rings A and B are the same size.

Embodiment 8 provides the compound of any one of Embodiments 1-7,wherein rings A and B are 5-membered rings.

Embodiment 9 provides the compound of any one of Embodiments 1-8,wherein at least one of rings A and B include at least one oxygen atom.

Embodiment 10 provides the compound of any one of Embodiments 1-9,wherein each of rings A and B include at least one oxygen atom.

Embodiment 11 provides the compound of any one of Embodiments 1-10,wherein each of rings A and B is a tetrahydrofuran ring, wherein eachcarbon atom shared by rings A and B has an oxygen atom alpha thereto.

Embodiment 12 provides the compound of any one of Embodiments 1-11,wherein each of the two hydrogen atoms on the carbon atoms shared byrings A and B have syn stereochemistry with respect to one another.

Embodiment 13 provides the compound of any one of Embodiments 1-12,wherein m=n.

Embodiment 14 provides the compound of any one of Embodiments 1-13,wherein m=n=1.

Embodiment 15 provides the compound of Embodiment 14, wherein each ofthe two ester substituents including R′ and R″ are alpha to a differentcarbon atom shared by each of rings A and B.

Embodiment 16 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 17 provides the compound of Embodiment 1, wherein the

Embodiment 18 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 19 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 20 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 21 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 22 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 23 provides the compound of Embodiment 1, wherein thecompound is

Embodiment 24 provides a method of making a polyisocyanate, comprising:a) contacting a compound having the structure

an acid anhydride having the structure

to provide a polyacid having the structure of Formula (I)

wherein R″ is —C(O)OH; b) contacting the polyacid and an acyl halidegenerator, to provide a polyacyl halide having the structure of Formula(I) wherein R″ is —C(O)X, wherein X is halide; and c) contacting thepolyacyl halide and an azide generator, under conditions suitable toyield a polyisocyanate having the structure of Formula (I) wherein R″ is—NCO; wherein fused rings A and B are each independently selected from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl, m and n are eachindependently 1-8, R′ is selected from the group consisting of(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and (C₂-C₁₀)alkynylene, whereinR′ is unsubstituted or substituted with at least one J, and fused ringsA and B are each independently unsubstituted or substituted with atleast one of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J, and wherein J independently ateach occurrence is selected from the group consisting of F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

Embodiment 25 provides the method of Embodiment 24, wherein m=n=1.

Embodiment 26 provides the method of any one of Embodiments 24-25,wherein the acid anhydride is succinic anhydride.

Embodiment 27 provides the method of any one of Embodiments 24-26,wherein the acyl halide generator is at least one of thionyl chloride,thionyl bromide, phosphorous pentachloride, phosphorus pentabromide,cyanuric fluoride, phosgene, diphosgene, triphosgene, oxalyl chloride,phosphorus tribromide, phosphorus trichloride, and phosphoryl chloride.

Embodiment 28 provides the method of any one of Embodiments 24-27,wherein the azide generator is at least one of sodium azide,trimethylsilyl azide, triethylsilyl azide, lithium azide, potassiumazide, tetrabutylammonium azide, tert-butyldimethylsilyl azide, andtert-butyldiphenylsilyl azide.

Embodiment 29 provides the method of any one of Embodiments 24-28,wherein contacting the polyacyl halide with an azide generator providesa polyacyl azide having the structure of Formula (I) wherein R″=—C(O)N₃,wherein the polyacyl azide undergoes a Curtius rearrangement to providethe polyisocyanate.

Embodiment 30 provides the method of any one of Embodiments 24-29,wherein the contacting the polyacyl halide and the azide generator isperformed in a biphasic solution comprising at least an aqueous phaseand an organic phase and optionally further comprising a phase transfercatalyst.

Embodiment 31 provides a polyurethane derived from the compound of anyone of Embodiments 1-23.

Embodiment 32 provides a polyurethane comprising a reaction product ofthe polyisocyanate of any one of Embodiments 1-23 with R″=—NCO and analcohol.

Embodiment 33 provides the polyurethane of Embodiment 32, wherein thealcohol comprises a polyol comprising a polyether polyol, a polyesterpolyol, or a combination thereof.

Embodiment 34 provides a method of making a polyurethane comprisingcontacting the polyisocyanate of any one of Embodiments 1-23 withR″=—NCO with an alcohol to provide a polyurethane.

Embodiment 35 provides the polyurethane of Embodiment 34, wherein thealcohol comprises a polyol comprising a polyether polyol, a polyesterpolyol, or a combination thereof.

Embodiment 36 provides a polyurethane comprising a plurality of subunitseach having the structure of Formula (II)

wherein fused rings A and B are each independently selected from(C₅-C₁₀)cycloalkyl and (C₂-C₁₀)heterocyclyl; m and n are eachindependently 1-8; R′ is selected from the group consisting of(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and (C₂-C₁₀)alkynylene, whereinR′ is unsubstituted or substituted with at least one J; fused rings Aand B are each independently unsubstituted or substituted with at leastone of J, (C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl,(C₁-C₁₀)haloalkyl, (C₁-C₁₀)alkoxy, (C₁-C₁₀)haloalkoxy,(C₁-C₁₀)cycloalkyl(C₀-C₁₀)alkyl, (C₁-C₁₀)heterocyclyl(C₀-C₁₀)alkyl,(C₁-C₁₀)aryl(C₀-C₁₀)alkyl, or (C₁-C₁₀)heteroaryl(C₀-C₁₀)alkyl; whereineach alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl,aryl, heterocyclyl, and heteroaryl is independently unsubstituted orfurther substituted with at least one J; and wherein J independently ateach occurrence is selected from the group consisting of F, Cl, Br, I,OR, CN, CF₃, OCF₃, R, O, S, C(O), S(O), methylenedioxy, ethylenedioxy,N(R)₂, SR, S(O)R, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R,C(S)R, C(O)OR, OC(O)R, OC(O)OR, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂NHC(O)R, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)C(O)N(R)₂,N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂,N(R)C(S)N(R)₂, N(C(O)R)C(O)R, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, andC(═NOR)R, wherein R is independently at each occurrence selected fromthe group consisting of hydrogen, (C₁-C₁₀)alkyl, (C₁-C₁₀)cycloalkyl,(C₁-C₁₀)cycloalkyl(C₁-C₁₀)alkyl, (C₁-C₁₀)aryl, (C₁-C₁₀)aralkyl,(C₁-C₁₀)heterocyclyl, (C₁-C₁₀)heterocyclyl(C₁-C₁₀)alkyl,(C₁-C₁₀)heteroaryl, and (C₁-C₁₀)heteroaryl(C₁-C₁₀)alkyl, wherein eachalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl,heterocyclylalkyl, heteroaryl, and heteroarylalkyl is independentlyunsubstituted or substituted with 1-3 J.

Embodiment 37 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 38 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 39 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 40 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 41 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 42 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 43 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 44 provides the polyurethane of Embodiment 36, whereinFormula (II) is:

Embodiment 45 provides a aqueous dispersion comprising the polyurethaneof any one of Embodiments 31-33 and 35-44.

Embodiment 46 provides the apparatus or method of any one or anycombination of Embodiments 1-45 optionally configured such that allelements or options recited are available to use or select from.

1. (canceled)
 2. A compound of Formula (I):

wherein fused rings A and B are each independently selected from(C₅-C₁₀)cycioalkyl and (C₂-C₁₀)heterocyclyl; m and n are eachindependently 1-8; R′ is selected from the group consisting of(C₂-C₁₀)alkanylene, (C₂-C₁₀)alkenylene, and (C₀-C₁₀)alkynylene, whereinR′ is unsubstituted or substituted; R″ is selected from the groupconsisting of —C(O)OH, —C(O)O⁻X⁺, —C(O)F, —C(O)Cl, —C(O)Br, —C(O)I,—C(O)N₃, and —NCO, wherein X⁺ is a counterion; and fused rings A and Bare each independently unsubstituted or substituted.
 3. The compound ofclaim 2, wherein R″ is —NCO.
 4. The compound of claim 2, wherein R′ isunsubstituted.
 5. The compound of claim 2, wherein R′ is —CH₂—CH₂—. 6.The compound of claim 2, wherein rings A and B are unsubstituted withthe exception of the ester substituents including R′ and R″.
 7. Thecompound of claim 2, wherein m=n=1, and one of the ester substituentsincluding R′ and R″ is alpha to at least one carbon atom shared by ringsA and B.
 8. The compound of claim 2, wherein rings A and B are the samesize.
 9. The compound of claim 2, wherein rings A and B are 5-memberedrings.
 10. The compound of claim 2, wherein each of rings A and Binclude at least one oxygen atom.
 11. The compound of claim 2, whereineach of rings A and B is a tetrahydrofuran ring, wherein each carbonatom shared by rings A and B has an oxygen atom alpha thereto.
 12. Thecompound of claim 2, wherein m=n=1.
 13. The compound of claim 12,wherein each of the two ester substituents including R′ and R″ are alphato a different carbon atom shared by each of rings A and B.
 14. Thecompound of claim 2, wherein the compound is:


15. The compound of claim 2, wherein the compound is:


16. The compound of claim 2, wherein the compound is:


17. The compound of claim 2, wherein the compound is:


18. The compound of claim 2, wherein the compound is:


19. The compound of claim 2, wherein the compound is:


20. The compound of claim 2, wherein the compound is:


21. The compound of claim 2, wherein the compound is: